Process for alkylating arylamines



Patented Dec. 18, 1945 PROCESS FOR. ALKYLATING ARYLAIVIINES Joseph B. Dickey, Rochester, N. Y., and James G.

McNally, Knoxville, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation oi New Jersey No Drawing. Application December 15, 1943,

Serial No. 514,424

3 Claims.

This invention relates to the alkylation of arylamines, and-more particularly to the catalytic alkylation of arylamines.

The N-alkylation of aryl amines by means by I means of alcohols or ethe-rs in the presence of certain catalysts is shown in U. S. Patent 2,017,051

f Arnold and Williams, U. 5. Patents 2,017,069

of Lazier, and 2,073,671 of Andrews. The catalysts shown in these patents all require to be debases having a hydrogen attached to the ring nitrogen, e. g. tetrahydroquinolinamay be alkylated according'to our invention.

The following examples are illustrative of the carrying out of our invention:

Example 1.Aniline and ethyl alcohol are charged into a shaking autoclave and boron tri-- fluoride is passed in until the desired amount is absorbed. The charge is heated and shaken for In addition to aromatic amines, heterocyclic posited on carriers: e. g., alumina on activated a number of hours, and then removed after coolcharcoal, or a phosphate on pumice. The preping. The reaction product is extracted with dilute aration of such a catalyst mass necessarily inalkali, and'fractionated. In addition to ethylvolves expense and inconvenience. aniline, diethylaniline and unreacted aniline, a We have discovered that boron trifluoride is small amount of high-boiling bases, boiling at an excellent catalyst for the N-alkylaticn of aryl 218-230" C-, W obtainedn five experiments, amines-by means of alcohols, ethers, or ether the results were as follows:

Gram-moles Percent yield Temp. Time Unw we an ea- 2.2 C. Hour: 2 10 2.0 215 15 12 1 2 10 1.0 215 lb 45 45 5 3 13 0.75 2l5 15 55 20 i3 a 13 0.15 180 11 09 0 20 3 13 1.0 180 24 00 0 2s alcohols. Boron trifluoride is a gas, and can be a It thus appears that while there is no correpassed directly into the mixture of aryl amine and lation between the results and the amount. of alcohol or ether in an autoclave. Alternatively. catalyst or the time of heating, f ormtaion of disince boron trifluoride forms complexes with alethylaniline is favored by a .high proportion of cohols, ethers, or amines, the boron trifluoride ethyl alcohol and inhibited by a low reaction temcan be passed into one of the starting materials perature. before the latter is put'into the autoclave. Example 2.279 g. (3.0 g.-moles) of aniline, Either primary or secondaryamines may be 384 g. (12.0 g.-moles) of methanol and 102 g. alkyiated. In the case of a primary amine, if di- (1.5 g.-moles) of boron trifluoride were heated in alkylation is desired, the proportion of alcohol or a shaking autoclave for 16 hours at 215 C. A etheris increased. Raising the temperature above 40 52% yield of dimethyl aniline and a small amount that necessary for N -alkylation may result in of methylaniline were obtained. The rest of the alkylation of the ring. For example, when aniline aniline did not react. was reacted with ethyl ether in the presence of Exampl g; (1.0 g.-mole) 0f aniline. 304 boron trifluoride to give ethylaniline and dig. (4.0 g.-moles) of ethylene glycol monomethyl ethylaniline, it was noted that at temperatures ether and 34 g. (0.5 mole) of boron trifluoride around 215 C. some ethylation of the ring also were heated in a shaking autoclave-at 200-205 C. took place. for 15 hours. The reaction product'was worked When the monomethyl ether of ethylene glycol up as in Example 1. A yield of dimethylwas employed as the alkylating agent, the prinaniline was obtained, together with 10-15% of cipal products were methylaniline and dimethyl- 50 resin, small amounts of B-hydroxyethylaniline, dianiline- Small amounts of p-hydroxyethylani- B-hydroxyethylaniline, p-methoxyethylaniline, line, di-p-hydroxyethylaniline, B-methoxyethyland di-p-methoxyethylaniline. 3% of unreacted aniline, and products boiling well above 325 C. aniline was recovered. were also formed. When the same process was carried out at a as temperature of C., no resin was formed, and

a good yield of methyl and dimethylaniline was obtained, together with a small amount of monopi-methoxyethylaniline. 540% of unreacted aniline was recovered.

Example 4.1g.-mole of aniline, 5 g.-moles of ethyl ether, and 0.5 mole of boron trifiuoride were heated in a shaking autoclave at 215 for 16 hours. The reaction product was worked up as in Example 1, and there was obtained a. 62% yield of ethylaniline, and a 25% yield of diethylaniline, together with 2% of unreacted aniline and a mixture of ethyl and diethylanilines containing one or more ethyl groups attached to the ring. By

dimethyl ether, cycloheicylethyl ether, or the like. Besides having the advantage of convenience in use, boron trifiuoride can be purchased and is potentially very cheap. It is not poisoned by imlowering the reaction temperature, the amount of this fraction was decreased.

Example 5.1 g.-mole of ethylaniline, 3 g.- moles of methanol, and 0.2 g.-niole of boron trifiuoride were heated in a shaking autoclave at 190 C. for 30 hours. An excellent yield of methylethylaniline was obtained.

purities, and can be readily recovered by means 0! calcium fluoride. (The mixture containing boron trifiuoride is extracted with an aqueous suspension of calcium fluoride. The suspension is then con centrated by evaporation, and treated with sulfuric acid.)

Crude alcohols, ethers, and aromatic amines can be used when boron trifiuoride is used as a catalyst, which isnot the case with the catalysts of the prior art. Moreover, higher yields of alkylated amines are obtained than when the prior art catalysts are used. It desired, both the amino Example 6.-1 g.-mole of aniline, 8 g.-moles of butyl alcohol, and 0.25 g.-mole of boron trifluo ride were heated in a shaking autoclave at C. for 48 hours. The reaction'product was worked up as in Example 1 to give a good yield of =butyl and dibutyl aniline.

Corresponding results were obtained with m-toluidine. 1

Example 7.1 g.-mole of aniline, 0.25 g.-mole of boron trifiuoride and 4 g.-moles of ethylene glycol were heated in a shaking autoclave at 180- for 18 hours. The reaction products were worked up as in Example 1 to give monoand di-B-hydroxy ethylaniline, together with smaller amounts of higher-boiling compounds.

In place of aniline we may use, for example, methyl aniline, o-, mand p-toluidine, the halogenated anilines, nitroaniline, a-naphthylamine, p-aminobenzene sulfonamlde, the xenylamines, aminofluorene, and th like, or we may use a heterocyclic base in which a hydrogen atom is attached to the ring nitrogen.

In place of the .alkylating agents mentioned in the examples, we may employ, for example, propyl alcohol, pentanol, cyclohexanol, heptyl alcohol, lauryl alcohol, -cety1 alcohol, p-phenyl ethanol, henzyl alcohol, diethylene glycol monoethyl ether, methylethyl ether, dipropyl ether, dibutyl ether,

group and the aromatic ring can be alkylated.

.What we claim as our invention and desire to be secured by Letters Patent or the United States is: g

1, A process for the N -alkylation of a compound selected from the group consisting of aromatic amines having at least one hydrogen atom attached to the amino nitrogen, and heterocyclic bases containing anitrogen atom in the ring and having a hydrogen atom attached to the ring nitrogen, which comprises heating this compound with a compound selected from the group consisting of alcohols, aliphatic and alicyclic ethers, and ether-alcohols, in the presence of boron trifiuoride as a. catalyst.

2. A process for the N-alkylation of an aromatic amine having at least one hydrogen atom attached to the amino nitrogen, which comprises heating the amine with a compound selected irom the group consisting of alcohols, aliphatic and alicyclic ethers, and ether-alcohols, in the presence of boron trifiuoride as a. catalyst.

3. A process tor'the N-alkylation of a heterocyclic base containing a nitrogen atom in the ring and having a hydrogen atom attached to the ring nitrogen, which comprises heating the heterocyclic base with a. compound selected from the group consisting of alcohols, aliphatic and aucyclic ethers, and ether-alcohols, in the presence of boron trifiuoride as a catalyst.

JOSEPH B. DICKEY. JAMES G. McNALLY. 

